CN103706346A - Method for improving activity of anthraquinone degradation product regeneration catalyst - Google Patents
Method for improving activity of anthraquinone degradation product regeneration catalyst Download PDFInfo
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- CN103706346A CN103706346A CN201310736807.7A CN201310736807A CN103706346A CN 103706346 A CN103706346 A CN 103706346A CN 201310736807 A CN201310736807 A CN 201310736807A CN 103706346 A CN103706346 A CN 103706346A
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Abstract
The invention discloses a method for improving the activity of an anthraquinone degradation product regeneration catalyst. The method mainly comprises the steps of performing in-situ regeneration on pseudo-boehmite serving as a catalyst precursor by a surface in-situ growth technology, so that the specific surface area and the pore volume of the catalyst can be enlarged; and preparing the supported type high-dispersion anthraquinone degradation product regeneration catalyst by a solid alkaline and catalyst doping and compounding technology. Therefore, rapid runoff of liquid active components can be avoided; furthermore, by virtue of the strong interaction between the active components and a carrier, the performance of active aluminum oxide can be kept for a long time, so that the service life of the anthraquinone degradation product regeneration catalyst is prolonged in a multiplied manner, and the catalyst can achieve high anthraquinone degradation product regeneration activity for a long time.
Description
Technical field
The invention belongs to field of new material preparation, relate to a kind of method that improves catalyst activity, be specifically related to a kind of method that improves regenerating anthraquinone degradation products catalyst activity.
Background technology
Anthraquinone is to prepare on a large scale in the world hydrogen peroxide (H
2o
2) main method, in this technique, anthraquinone and hydrogen reaction generate hydrogen anthraquinone, then by oxygen or air oxidation, make hydrogen anthraquinone change anthraquinone into again, simultaneously Hydrogen Peroxide.Due to the generation of side reaction, in working solution, form gradually some and do not possessed the degradation product of hydrogen peroxide manufacture ability, valuable effective anthraquinone content is constantly reduced.In industrial production, conventionally with the activated alumina of load caustic soda, anthraquinone degradation products is regenerated at present, because of loss gradually and the continuous deactivation of activated alumina of caustic soda, the service life of regenerated catalyst is very short, is generally no more than 50 days.Owing to adopting poor efficiency regenerating anthraquinone degradation products catalyst, directly increase the production cost of hydrogen peroxide, and in Hydrogen Peroxide Industry, caused annual number in the waste of the fine aluminum soil resource of ten thousand tons, do not meet National Sustainable Development Strategies.
Alkalescence activated alumina is current anthraquinone production H
2o
2the most frequently used regenerating anthraquinone degradation products catalyst, conventionally there are bar shaped or spherical two kinds, although alkaline activated alumina catalyst has certain power of regeneration to anthraquinone degradation products, meet current demand of industrial production, but owing to using liquid caustic soda action activity component, inevitably have the quick leakage of liquid caustic soda active component, cause regeneration activity to decline rapidly, service life is short.Therefore a kind of new method that can overcome above-mentioned defect raising anthraquinone degradation products catalyst activity is called those skilled in the art's technical problem urgently to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is, the shortcoming existing for above prior art, a kind of method that improves regenerating anthraquinone degradation products catalyst activity is proposed, it is raw material that the method be take the direct fast dewatering of aluminium hydroxide, use surface in situ growing technology, adopt solid base and catalyst doping compounded technology, the hydrogenation degradation product reducing/regenerating improving in anthraquinone producing hydrogen peroxide production procedure is the activity of effective anthraquinone catalyst, make more than anthraquinone degradative reduction regeneration amount reaches 5 g/L, to extend to service life more than 100 days.
The technical scheme that the present invention solves above technical problem is:
A method that improves regenerating anthraquinone degradation products catalyst activity, comprises the steps:
(1) aluminium hydroxide of take containing 3-8wt% adsorption water is sent into drying tower as raw material and is dried, and being dried to adsorption water content is after 0.1-1%, to send into pulverizer to pulverize again;
(2) raw material after pulverizing in step (1) being sent into fast de-stove carries out fast dewatering and obtains fast shedding; When fast de-stove carries out fast dewatering, igloss is controlled at 5-9wt%;
(3) fast shedding being mixed with deionized water and put in autoclave, is 170 ℃ in temperature, under pressure 0.8 MPa, carries out hydrothermal treatment consists, and keeps carrying out for 0-36 hour nature growth in situ and obtain former powder; The addition of deionized water is 2 times of fast shedding volume;
(4) former powder and solid base are fully mixed and add rare nitric acid to mediate again, then through the slivering of filter press filter pressing; The solubility quality percentage composition of solid base is 1-5wt%, and rare nitric acid solubility mass percentage content is 5-10wt%, and the bar diameter that press filtration is made is at 2-5mm;
(5) bar of press filtration in step (4) being made is sent in drying room, at 120 ℃, dries 5-20h, then carries out quick roasting, and sintering temperature is 550-600 ℃, and roasting 5-8h, obtains Al
2o
3catalyst, Al
2o
3pore volume>=the 0.55ml/g of catalyst, specific area>=180 m
2/ g, regeneration activity>=5 g/L.
The technical scheme that the present invention further limits is:
In the method for aforementioned raising anthraquinone degradation products catalyst activity, after pulverizing in step (1), the granularity of aluminium hydroxide is 400-800 order.
In the method for aforementioned raising anthraquinone degradation products catalyst activity, Al in step (5)
2o
3its crystal formation of catalyst is γ type, Al
2o
3the pore volume of catalyst is: 0.55-1.0ml/g; Specific area is: 200-250 m
2/ g; Regeneration activity: 5-10 g/L.
In the method for aforementioned raising anthraquinone degradation products catalyst activity, roasting in step (5) is to carry out in activation furnace, activation furnace is full-automatic activation furnace, all control systems are by manually upgrading to full-automatic chain control, thermometric, pressure measurement and material drain system are all realized chain, all by computer, automatically controlled, stopped the impact of human factor.
The invention has the beneficial effects as follows:
(1) the present invention improves and in the method for anthraquinone degradation products catalyst activity, first raw material is sent into drying tower containing the aluminium hydroxide of adsorption water and carry out drying and dehydrating, guarantee that the fast shedding after pulverizing is dried and avoids sticking in the loss that causes raw material on pulverizer in crushing process, raises the cost.
(2) in the present invention, use hydrothermal treatment consists to combine catalyst is processed with surface in situ growing technology, under hydrothermal condition, particle has carried out growth in situ increases crystal grain, thereby causes space to increase, and prepares large pore volume, high-ratio surface activated alumina.
(3) in the present invention, use solid base to replace liquid caustic soda to adopt doping compounded technology as active component and with catalyst, not only can avoid the quick leakage of liquid caustic soda active component, and by the strong interaction of active component and carrier, the performance of activated alumina is kept for a long time, thereby significantly improved the service life of regenerating anthraquinone degradation products catalyst, and it is active to make catalyst have for a long time higher regenerating anthraquinone degradation products.
(4) roasting of step of the present invention (5) is to carry out in full-automatic activation furnace, has replaced the manual control activation furnace of current use, and stabilized product quality soaks for a long time not deliquescing, not efflorescence in anthraquinone working solution; Improve aluminium oxide active, strengthen anthraquinone derivative degradation product power of regeneration, extended the service life of catalyst.
(5) bar shaped catalyst pore volume>=0.55 ml/g preparing in the present invention; Specific area>=180 m
2/ g; Regeneration activity>=5 g/L; Service life>=100 day, have effectively suppressed the generation of side reaction, do not affect the production of hydrogen peroxide, have reduced the production cost of hydrogen peroxide.
Accompanying drawing explanation
Fig. 1 is the XRD figure that the embodiment of the present invention detects activated sample.
Fig. 2 is the comparison schematic diagram of gained catalyst of the present invention and traditional catalyst activity.
Fig. 3 is the activity curve of regenerating anthraquinone degradation products catalyst in the present invention.
The specific embodiment
embodiment 1
The present embodiment provides a kind of method that improves regenerating anthraquinone degradation products catalyst activity, comprises the steps:
(1) aluminium hydroxide of take containing 3wt% adsorption water is sent into drying tower as raw material and is dried, and sends into pulverizer after being dried to adsorption water content and being 0.5% to pulverize again;
(2) raw material after pulverizing in step (1) being sent into fast de-stove carries out fast dewatering and obtains fast shedding; When fast de-stove carries out fast dewatering, igloss is controlled at 8wt%;
(3) by fast shedding and volume, be that the deionized water of 2 times of fast shedding volumes is mixed and put in autoclave in temperature, to be 170 ℃, under pressure 0.8 MPa, to carry out hydrothermal treatment consists, hydrothermal treatment consists 12h carries out nature growth in situ and obtains former powder;
(4) solid base that is 1wt% by former powder with solubility quality percentage composition fully mixes and adds solubility mass percent is again that rare nitric acid of 8wt% is mediated, and then through filter press press filtration, makes the bar that diameter is 3mm;
(5) bar after the press filtration in step (4) is sent in drying room, at 120 ℃, dried 9h, then in full-automatic activation furnace, carry out roasting, sintering temperature is 550 ℃, roasting 7h.
In the present embodiment, in step (1), after pulverizing, the granularity of aluminium hydroxide is 600 orders.
In the present embodiment, Al in step (3) after measured
2o
3its crystal formation of catalyst is γ type, Al
2o
3the pore volume of catalyst is: 0.56ml/g; Specific area is: 240 m
2/ g; Regeneration activity 5.8 g/L.
Embodiment 2
The present embodiment provides a kind of method that improves regenerating anthraquinone degradation products catalyst activity, comprises the steps:
(1) aluminium hydroxide of take containing 6wt% adsorption water is sent into drying tower as raw material and is dried, and sends into pulverizer after being dried to adsorption water content and being 0.2% to pulverize again;
(2) raw material after pulverizing in step (1) being sent into fast de-stove carries out fast dewatering and obtains fast shedding; When fast de-stove carries out fast dewatering, igloss is controlled at 5wt%;
(3) fast shedding being mixed in threading autoclave with the deionized water of 2 times of fast sheddings of volume is 170 ℃ in temperature, under pressure 0.8 MPa, carries out hydrothermal treatment consists, and hydrothermal treatment consists keeps carrying out nature growth in situ during 24 hours and obtains former powder;
(4) solid base that is 3wt% by former powder with solubility quality percentage composition fully mixes and adds solubility mass percent is again that rare nitric acid of 5wt% is mediated, and then through filter press press filtration, makes the bar that diameter is 4mm;
(5) bar after the press filtration in step (4) is sent in drying room, at 120 ℃, dried 15h, then carry out quick roasting, sintering temperature is 580 ℃, roasting 5h.
In the present embodiment, in step (1), after pulverizing, the granularity of aluminium hydroxide is 640 orders.
In the present embodiment, Al in step (3) after measured
2o
3its crystal formation of catalyst is γ type, Al
2o
3the pore volume of catalyst is: 0.58ml/g; Specific area is: 220 m2/g; Regeneration activity 6.1 g/L.
embodiment 3
The present embodiment provides a kind of method that improves anthraquinone degradation products catalyst activity, comprises the steps:
(1) aluminium hydroxide of take containing 8wt% adsorption water is sent into drying tower as raw material and is dried, and sends into pulverizer after being dried to adsorption water content and being 0.6% to pulverize again;
(2) raw material after pulverizing in step (1) being sent into fast de-stove carries out fast dewatering and obtains fast shedding; When fast de-stove carries out fast dewatering, igloss is controlled at 6wt%;
(3) fast shedding being mixed in threading autoclave with the deionized water of 2 times of fast sheddings of volume is 170 ℃ in temperature, under pressure 0.8 MPa, carries out hydrothermal treatment consists, and hydrothermal treatment consists keeps carrying out nature growth in situ during 36 hours and obtains former powder;
(4) solid base that is 5wt% by former powder with solubility quality percentage composition fully mixes and adds solubility mass percent is again that rare nitric acid of 10wt% is mediated, and then through filter press press filtration, makes the bar that diameter is 5mm;
(5) bar after the press filtration in step (4) is sent in drying room, at 120 ℃, dried 17h, then carry out quick roasting, sintering temperature is 600 ℃, roasting 6h.
In the present embodiment, in step (1), after pulverizing, the granularity of aluminium hydroxide is 700 orders.
In the present embodiment, Al in step (3) after measured
2o
3its crystal formation of catalyst is γ type, Al
2o
3the pore volume of catalyst is: 0.59ml/g; Specific area is: 210 m2/g; Regeneration activity 6.3 g/L.
Embodiment detects:
By the step in embodiment 2, operate, the activated sample that the D8 Advance X-ray diffractometer that utilizes Bruker AXS company to produce is 0,12,24,36 hour in the hydrothermal treatment consists time is carried out its crystalline phase of X-ray diffraction analysis (voltage 40 kV, electric current 40 mA, 0.02 ° of s-1 of sweep speed), result as shown in Figure 1.
Fig. 1 is the XRD figure of activated sample, as seen from the figure: sample is in 2 θ=37.11
., 39.49
°, 45.95
°with 66.91
°there is respectively the characteristic peak that diffracted intensity is larger in place, with the γ-Al of (10-0425) on JCPDS standard card
2o
3consistent, interpret sample is after roasting, and crystalline phase is γ-Al
2o
3.These sample structure evolution features can find out from its diffraction peaks broadening, and the reduction along with the half-peak breadth of diffraction maximum, is accompanied by the increase of crystallite dimension, can calculate γ-Al by Scherrer formula
2o
3grain size on (640) face, in Table 1.
The crystallite dimension of the different hydrothermal treatment consists of table 1 activated sample under the time
| The hydrothermal treatment consists time (h) | 0 | 12 | 24 | 36 |
| γ-Al 2O 3Crystallite dimension (nm) | 2.5 | 2.7 | 3.0 | 3.4 |
As shown in Table 1, the length of hydrothermal treatment consists time is to γ-Al
2o
3crystallite dimension has certain influence, and along with the prolongation of hydrothermal treatment consists time, crystallite dimension increases to some extent.This explanation is under hydrothermal condition, and growth in situ has occurred particle.
Specific surface, pore volume utilize the ASAP2010 type instrument adsorption instrument that U.S. Merck & Co., Inc produces to adopt cryogenic nitrogen physisorphtion to measure, by the area of desorption peaks, calculated the adsorbance of nitrogen, by BET equation, calculate specific surface again, in embodiment 2, the hydrothermal treatment consists time tested in the time of 0,12,24,36 hour, and result is as following table 2:
The impact of different hydrothermal treatment consists time of table 2 on specific surface area of catalyst and pore volume
| The hydrothermal treatment consists time (h) | 0 | 12 | 24 | 36 |
| γ-Al 2O 3Specific area (m 2/g） | 230 | 221 | 210 | 200 |
| γ-Al 2O 3Pore volume (ml/g) | 0.54 | 0.56 | 0.59 | 0.62 |
As shown in Table 2, along with the prolongation of hydrothermal treatment consists time, specific area declines to some extent, and pore volume increases to some extent.This is mainly because under hydrothermal condition, and particle has carried out growth in situ increases crystal grain, thus the cause that causes mesopore to increase.
It is composite that fast shedding after water intaking heat treatment 24 h and solid base (representing with M) carry out different solubility 1%, 2%, 3.5%, 5%, uses respectively M
1, M
2, M
3, M
4represent traditional catalyst M again
0represent, adopt the activity of the JP-303 polarographic analyze mensuration catalyst of Chengdu Instruement Factory's production, result as shown in Figure 2.
As shown in Figure 2, the adding of solid base, its activity is compared with traditional catalyst (M
0) be significantly improved, and along with solid base content increases, activity also has obvious increase.But research is discovery simultaneously, and solid base joins a certain amount of, can affect catalyst strong.
50
ounder C water bath condition, anthraquinone degraded working solution carries out test in service life with the certain speed reaction tube of flowing through, regeneration (H4) the EAQ content of take is index, adopt the activity of the JP-303 polarographic analyze mensuration catalyst of Chengdu Instruement Factory's production, as shown in Figure 3, after 96 h, performance reaches stable, and activity data is high more than 1 times compared with traditional catalyst (1.0%).As can be seen from the table, after use 1440 h, loss of active component is not obvious, and activity stability is good, can use more than 100 days, has therefore possessed the bright outlook using as industrial catalyst.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (4)
1. a method that improves anthraquinone degradation products catalyst activity, is characterized in that, comprises the steps:
(1) aluminium hydroxide of take containing 3-8wt% adsorption water is sent into drying tower as raw material and is dried, and being dried to adsorption water content is after 0.1-1%, to send into pulverizer to pulverize again;
(2) raw material after pulverizing in step (1) being sent into fast de-stove carries out fast dewatering and obtains fast shedding; When described fast de-stove carries out fast dewatering, igloss is controlled at 5-9wt%;
(3) fast shedding being mixed with deionized water and put in autoclave, is 170 ℃ in temperature, under pressure 0.8 MPa, carries out hydrothermal treatment consists, and keeps carrying out for 0-36 hour nature growth in situ and obtain former powder; The addition of described deionized water is 2 times of fast shedding volume;
(4) former powder and solid base are fully mixed and add rare nitric acid to mediate again, then through the slivering of filter press filter pressing; The solubility quality percentage composition of described solid base is 1-5wt%, and rare nitric acid solubility mass percentage content is 5-10wt%, and the bar diameter that press filtration is made is at 2-5mm;
(5) bar of press filtration in step (4) being made is sent in drying room, at 120 ℃, dries 5-20h, then carries out quick roasting, and sintering temperature is 550-600 ℃, and roasting 5-8h, obtains Al
2o
3catalyst, described Al
2o
3pore volume>=the 0.55ml/g of catalyst, specific area>=180 m
2/ g, regeneration activity>=5 g/L.
2. the method for raising regenerating anthraquinone degradation products catalyst activity as claimed in claim 1, is characterized in that, after pulverizing in described step (1), the granularity of aluminium hydroxide is 400-800 order.
3. the method for raising regenerating anthraquinone degradation products catalyst activity as claimed in claim 1, is characterized in that, Al in step (5)
2o
3its crystal formation of catalyst is γ type, Al
2o
3the pore volume of catalyst is: 0.55-1.0ml/g; Specific area is: 200-250 m
2/ g; Regeneration activity: 5-10 g/L.
4. the method for raising regenerating anthraquinone degradation products catalyst activity as claimed in claim 1, is characterized in that, the roasting in step (5) is to carry out in activation furnace, and described activation furnace is that thermometric, pressure measurement and material drain system are all realized chain full-automatic activation furnace.
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Cited By (6)
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|---|---|---|---|---|
| CN107570128A (en) * | 2016-07-05 | 2018-01-12 | 江苏中科睿赛污染控制工程有限公司 | A kind of industrial waste Al2O3Bead regenerative system and renovation process |
| CN109772464A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of solid base and its preparation method and application |
| CN109806875A (en) * | 2019-02-26 | 2019-05-28 | 浙江巴陵恒逸己内酰胺有限责任公司 | It is catalyzed the regeneration method of catalyst of regenerating anthraquinone degradation products and preparation method thereof and cycle working fluid |
| CN110102276A (en) * | 2019-05-20 | 2019-08-09 | 浙江恒澜科技有限公司 | The regeneration method of catalyst and preparation method thereof and anthraquinone degradation products |
| CN110327907A (en) * | 2019-04-22 | 2019-10-15 | 北京化工大学 | A kind of efficient regenerating anthraquinone degradation products catalyst and preparation method thereof |
| CN113289599A (en) * | 2021-06-07 | 2021-08-24 | 北京化工大学 | Silicate/alumina composite regenerated catalyst and preparation method and application thereof |
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| CN109806875A (en) * | 2019-02-26 | 2019-05-28 | 浙江巴陵恒逸己内酰胺有限责任公司 | It is catalyzed the regeneration method of catalyst of regenerating anthraquinone degradation products and preparation method thereof and cycle working fluid |
| CN110327907A (en) * | 2019-04-22 | 2019-10-15 | 北京化工大学 | A kind of efficient regenerating anthraquinone degradation products catalyst and preparation method thereof |
| CN110102276A (en) * | 2019-05-20 | 2019-08-09 | 浙江恒澜科技有限公司 | The regeneration method of catalyst and preparation method thereof and anthraquinone degradation products |
| CN113289599A (en) * | 2021-06-07 | 2021-08-24 | 北京化工大学 | Silicate/alumina composite regenerated catalyst and preparation method and application thereof |
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| CN103706346B (en) | 2015-09-16 |
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